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Palladium-catalyzed multi-component Heck alkynylcarbonylation of unactivated alkenes for synthesis of β,γ-alkynoates
Organic Chemistry Frontiers ( IF 5.4 ) Pub Date : 2024-05-01 , DOI: 10.1039/d4qo00504j
Xin Peng 1 , Huanliang Hong 1 , Li Wang 1 , Lu Chen 1 , Jinbao Peng 1 , Yibiao Li 1, 2 , Huanfeng Jiang 3
Affiliation  

Controlling the selectivity of reactions of palladium catalysts with various substrates is challenging. Herein, a general and unprecedented Pd-catalysed four-component inter-molecular Heck alkynylcarbonylation involving haloalkynes, alkenes, carbon monoxide (CO) and alcohols based on a molecular queuing strategy is presented. This efficient methodology proceeds via overall multiple Csp–Csp3 bond and C–O bond formations and provides a divergent approach for the efficient and selective construction of multi-substituted β,γ-alkynoates under mild reaction conditions. Experimental and density functional theory calculation results demonstrate that high selectivity olefin insertion and the following CO insertion are crucial catalytic steps.

中文翻译:

钯催化未活化烯烃的多组分 Heck 炔基羰基化反应合成 β,γ-炔酸酯

控制钯催化剂与各种底物的反应选择性具有挑战性。在此,提出了一种基于分子排队策略的通用且前所未有的 Pd 催化四组分分子间 Heck 炔基羰基化反应,涉及卤代炔、烯烃、一氧化碳 (CO) 和醇。这种有效的方法通过总体上多个 Csp-Csp 3键和 C-O 键的形成进行,并为在温和反应条件下高效、选择性地构建多取代 β,γ-炔酸酯提供了一种不同的方法。实验和密度泛函理论计算结果表明,高选择性烯烃插入和随后的CO插入是关键的催化步骤。
更新日期:2024-05-01
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